US4876396A - Selective chlorination of phenols - Google Patents
Selective chlorination of phenols Download PDFInfo
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- US4876396A US4876396A US07/078,771 US7877187A US4876396A US 4876396 A US4876396 A US 4876396A US 7877187 A US7877187 A US 7877187A US 4876396 A US4876396 A US 4876396A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
Definitions
- the present invention relates to the selective chlorination of phenolic compounds with gaseous chlorine, in the ortho-position relative to the hydroxyl group.
- German patent application No. 3,318,791 describes a selective process for the chlorination of phenol into 2-chlorophenol, in a perchlorinated apolar solvent and in the presence of a branched amine.
- a major object of the present invention is the provision of improved process for the selective chlorination of phenolic compounds with gaseous chlorine, one wherein the reaction is carried out in a molten reaction medium and in the presence of an amine.
- the present invention features a process for the selective chlorination, in the ortho-position relative to the hydroxyl group, of phenolic compounds having the general formula (I): ##STR1## in which R 2 is a halogen atom; an alkyl group having from 1 to 4 carbon atoms; an alkoxy group having from 1 to 4 carbon atoms; an acyloxy group having from 2 to 4 carbon atoms; an acyl group having from 2 to 4 carbon atoms; a carboxylic acid group; an ester group --COOR 5 , wherein R 5 is a straight or branched chain alkyl radical having from 1 to 4 carbon atoms; a nitrile group; an OH group; or a --CHO group; R 1 is a hydrogen atom or one of the substituents R 2 ; R 3 and R 4 , which may be identical or different, are each a hydrogen atom or one of the substituents R 2 ; in a molten reaction medium, with gaseous chlorine, and where
- amine is defined as any compound, liquid or solid under the operating conditions of the process, which comprises one or several amine functions.
- Such a compound may also contain one or several other functional groups, such as, for example, hydroxyl, carboxylic acid, carboxylic acid ester, amide or imine.
- Ammonia is also considered to be an amine for purposes of the present invention.
- the amines used may also be introduced in the form of their respective chlorohydrates.
- the amine catalysts are advantageously amines of the formula (II): ##STR2## in which R 6 , R 7 and R 8 , which may be identical or different, are each a straight-chain alkyl radical having from 3 to 12 carbon atoms, or a tertiary alkyl radical having from 4 to 12 carbon atoms, with the proviso that such alkyl radicals may contain one or two oxygen bridges, --O--, or a hydroxyl, amine, carboxylic acid, carboxylic acid ester, amide or imine group; a phenyl radical, a cyclohexyl radical, a cycloheptyl radical, a cyclopentyl radical, or a phenylalkyl, cyclohexylalkyl, cycloheptylalkyl or cyclopentylalkyl radical, the alkyl part of which comprises 1 to 4 carbon atoms; and with the further pro
- primary amines such as n-propylamine, isopropylamine, isobutylamine, n-butylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methylbutylamine, n-hexylamine, 2-ethylhexylamine, aniline, laurylamine, cyclohexylamine, cyclopentylamine, benzylamine, guanidine, acetamidine, glycine ethyl ester, ethanolamine, ethylenediamine, hexamethylenediamine, N-aminoethylpyrrolidine, pyrazoline, lysine, N-aminoethylpyrrolidine, lysine, N-aminomorpholine and N-aminopiperidine;
- primary amines such as n-propylamine, isopropylamine, isobutylamine, n-buty
- secondary amines such as dibutylamine, dipropylamine, methylpropylamine, methylbutylamine, methylisobutylamine, methyltert-butylamine, methylbenzylamine, piperidine, diisopropylamine, diisobutylamine, ditert-butylamine, 1-methylcyclopentylamine, 1-methylcyclohexylamine, dicyclohexylamine, morpholine, imidiazole, pyrrolidine, imidazolidine, piperazine, and indole;
- secondary amines such as dibutylamine, dipropylamine, methylpropylamine, methylbutylamine, methylisobutylamine, methyltert-butylamine, methylbenzylamine, piperidine, diisopropylamine, diisobutylamine, ditert-butylamine, 1-methylcyclopentylamine, 1-methylcyclohexylamine,
- tertiary amines such as triethylamine, tributylamine, pyridine, tris(3,6-dioxaheptyl)amine and 1,8-diaza-bicyclo[5,4,0]7-undecene;
- amino compounds such as hydrazine or its derivatives, in particular derivatives obtained by the substitution of one or two hydrogen atoms by alkyl, aryl, cycloaliphatic or heterocyclic radicals.
- the catalytically effective amount of the amine used in the process of the invention may vary over very wide limits.
- the reaction mixture constitutes, by weight relative to the weight of the reaction mixture, from 0.005% to 5% thereof.
- it constitutes, by weight relative to the weight of the reaction mixture, from 0.01 to 2.0% by weight of the amine relative to the reaction mixture will be employed, in order to provide sufficient efficacy, without using an excessive amount of the amine which does not concurrently permit any additional benefit or advantage.
- R 7 and R 8 which may be identical or different, are each a hydrogen atom, with the proviso that both R 1 and R 8 are not hydrogen; a straight-chain alkyl radical having from 1 to 10 carbon atoms; a secondary alkyl radical having from 3 to 10 carbon atoms; a tertiary alkyl radical having from 4 to 10 carbon atoms; a cyclohexyl or cyclopentyl radical; a phenyl radical; or a benzyl or phenethyl radical;
- R 7 and R 8 may alternatively form, together with the nitrogen atom from which they depend, and with another nitrogen atom and/or oxygen atom, a heterocycle which is saturated or which has one or several double bonds.
- Either or both R 7 and R 8 may contain one or several amine, hydroxyl or carboxylic ester groups.
- a secondary alkyl radical having from 3 to 10 carbon atoms such as isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-octyl, 3-octyl, 4-octyl, 2-nonyl, 3-nonyl, 4-nonyl, 5-nonyl, 2-decyl, 3-decyl, 4-decyl and 5-decyl; a cyclohexyl or cyclopentyl radical.
- heterocycles where R 7 and R 8 form, together with the nitrogen atom from which they depend, a heterocycle optionally containing another nitrogen or oxygen atom.
- Exemplary of such secondary amines diisopropylamine, diisobutylamine, dicyclohexylamine, morpholine and imidazole are representative.
- hexamethylenediamine N-aminoethylpyrrolidine
- pyrazoline N-aminomorpholine
- N-amino piperidine N-amino piperidine
- the phenolic compounds of the formula (I), for which the subject process is most valuable, are those in which R 2 is a chlorine atom, a fluorine atom or a bromine atom; a methoxy or ethoxy group; an aldehyde group; an OH group; a CN group; an acetoxy group; an ester group --COOR 5 , wherein R 5 is a methyl or ethyl group; or an acyl group having from 2 to 4 carbon atoms; R 1 is a hydrogen atom, a methyl, ethyl, propyl, isopropyl or tert-butyl group, or one of the substituents R 2 ; at least one of R 3 and R 4 is a hydrogen atom, and the other either a hydrogen atom or one of the substituents R 2 .
- Exemplary of the phenolic compounds of the formula (I), representative are: 4-chlorophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2-chloro-4-fluorophenol, 4-chloro-2-fluorophenol, 2-bromo-4-chlorophenol, 4-bromo-2-chlorophenol, 2-chloro-4-methoxyphenol, 4-chloro-2-methoxyphenol, 4-chloro-2-methylphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-hydroxyacetophenone, 4-hydroxybenzonitrile, 3-chloro-4-hydroxybenzaldehyde, and 5-chloro-2-hydroxybenzaldehyde.
- the process according to this invention has several advantages.
- One of these advantages is its intramolecular selectivity; when it is applied to a phenolic compound of formula (I) in which at least one of the meta-positions of the hydroxyl group is unsubstituted, essentially only the ortho-positions of the OH are chlorinated, whereas in the absence of the amine, a not insignificant amount of 3-chlorophenol or of the corresponding 5-chlorophenol is always formed, which is then very difficult to separate. Additionally, these compounds may be disadvantageous for certain applications.
- Another very valuable advantage relates to the intermolecular selectivity of the process: if the process is employed with a mixture of a phenolic compound of formula (I) and one or more other phenolic compounds (such as, for example, position isomers of said phenolic compound of formula (I)) which do not correspond to the formula (I), it is mostly the phenolic compound of formula (I) which is chlorinated, whereas the other phenolic compound(s) are but slightly modified.
- the process of the invention may advantageously be applied to a mixture of 2,4-dichlorophenol and 2,6-dichlorophenol; 2,4,6-trichlorophenol is obtained from 2,4-dichlorophenol, whereas the 2,6-dichlorophenol, which is only slightly modified, may be relatively easily separated from the final reaction mixture.
- Another advantage of the subject process is the fact that the reaction of the gaseous chlorine and of the phenolic compound of the formula (I) is substantially complete, whereas, in the absence of the amine, a significant amount of the chlorine does not react.
- the problems of recycling of the excess chlorine, or of treating the gaseous effluents become less difficult to solve.
- the amount of chlorine used in the process of the invention principally depends upon the desired degree of conversion of the phenolic compound (I).
- the chlorine may be used as such, or diluted with an inert gas, such as, for example, nitrogen.
- an inert gas such as, for example, nitrogen.
- the temperature at which the process of the invention is carried out is generally less than or equal to 150° C. Moreover, the lower limit of the temperature zone depends on the melting point of the phenolic compound (I), or mixture of phenolic compounds.
- This temperature typically ranges from the melting point of the reaction mixture to 120° C., these limits, however, not being critical.
- the temperature was raised to 70° C. under stirring, such that the mixture was liquid and the introduction of gaseous chlorine was then initiated at a flow rate of 5 liters/hour.
- reaction mass 47.21 g was obtained, which was analyzed by gas chromatography in the presence of an internal standard.
- Example 1 The following materials were introduced into a 200-cm 3 glass reactor equipped as indicated in Example 1:
- the reaction was carried out as in Example 1 at 70° C., with a 50/50 mixture of 2,4-dichlorophenol and 2,6-dichlorophenol.
- the gaseous chlorine was introduced at a flow rate of 5 l/h and the amount introduced was such that the molar ratio of chlorine: 2,4-dichlorophenol was 0.95.
- diisopropylamine 0.042 g (0.42 millimole, which is, 0.1% by weight relative to the dichlorophenols);
- the temperature was raised to 70° C., under stirring, such that the mixture was liquid and the introduction of gaseous chlorine was initiated at a flow rate of 5 liters/hour.
- the period of chlorination carried out at 70° C. was 3 hours, which corresponded to 670 millimoles of chlorine introduced.
- the reaction was therefore carried out with a 10% excess of chlorine relative to the 2,4-dichlorophenol.
- reaction mass was obtained, which was analyzed by gas chromatography in the presence of an internal standard.
- 2,4,5-Trichlorophenol concentration less than 0.001% by weight in the reaction mass (estimated at 0.0007%).
- Example 15 was repeated, with a twenty times higher concentration of diisopropylamine.
- 2,4,5-Trichlorophenol concentration less than 0.001% by weight in the reaction mass (estimated at 0.0004%).
- Example 15 was repeated without diisopropylamine.
- Control experiment B was repeated, but the supply of chlorine was terminated when the molar ratio of chlorine introduced/2,4-dichlorophenol added was equal to 1.1 (which represented a 10% excess of chlorine relative to the stoichiometric quantity).
- Table (VI) compiles the characteristics of the different examples, together with the results obtained.
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Abstract
Phenolic compounds and mixtures thereof, e.g., admixture of 2,4-dichlorophenol and 2,6-dichlorophenol, are selectively chlorinated at a position ortho to a hydroxyl function thereof, by reacting such phenolic compound with gaseous chlorine, in a molten reaction medium, in the presence of a catalytically effective amount of a primary, secondary or tertiary amine.
Description
This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 909,177 filed Sept. 19, 1986 now abandoned.
1. Field of the Invention
The present invention relates to the selective chlorination of phenolic compounds with gaseous chlorine, in the ortho-position relative to the hydroxyl group.
2. Description of the Prior Art
In the preparation of chlorophenols by chlorination of phenol, isomers are produced at different stages of the reaction, ultimately giving rise to many different compounds, which must then be separated by procedures which are both expensive and difficult. Moreover, the ratios of the different isomers do not necessarily correspond to those which would be economically viable, taking into account the existing markets.
Therefore, it appeared desirable to provide selective chlorination processes, especially for selective chlorination in the ortho-position, or in the para-position, relative to the hydroxyl group of the phenolic compound.
Thus, published German patent application No. 3,318,791 describes a selective process for the chlorination of phenol into 2-chlorophenol, in a perchlorinated apolar solvent and in the presence of a branched amine.
However, the use of a solvent in an industrial chlorination process is ofttimes problematical, providing such difficulties as, for example, the need for a larger reactor volume and a more difficult separation of the reaction products.
Accordingly, a major object of the present invention is the provision of improved process for the selective chlorination of phenolic compounds with gaseous chlorine, one wherein the reaction is carried out in a molten reaction medium and in the presence of an amine.
Briefly, the present invention features a process for the selective chlorination, in the ortho-position relative to the hydroxyl group, of phenolic compounds having the general formula (I): ##STR1## in which R2 is a halogen atom; an alkyl group having from 1 to 4 carbon atoms; an alkoxy group having from 1 to 4 carbon atoms; an acyloxy group having from 2 to 4 carbon atoms; an acyl group having from 2 to 4 carbon atoms; a carboxylic acid group; an ester group --COOR5, wherein R5 is a straight or branched chain alkyl radical having from 1 to 4 carbon atoms; a nitrile group; an OH group; or a --CHO group; R1 is a hydrogen atom or one of the substituents R2 ; R3 and R4, which may be identical or different, are each a hydrogen atom or one of the substituents R2 ; in a molten reaction medium, with gaseous chlorine, and wherein the reaction is carried out in the presence of a catalytically effective amount of a primary, secondary or tertiary amine.
The term "amine" is defined as any compound, liquid or solid under the operating conditions of the process, which comprises one or several amine functions.
Such a compound may also contain one or several other functional groups, such as, for example, hydroxyl, carboxylic acid, carboxylic acid ester, amide or imine.
Ammonia is also considered to be an amine for purposes of the present invention.
The amines used may also be introduced in the form of their respective chlorohydrates.
More particularly according to the present invention, the amine catalysts are advantageously amines of the formula (II): ##STR2## in which R6, R7 and R8, which may be identical or different, are each a straight-chain alkyl radical having from 3 to 12 carbon atoms, or a tertiary alkyl radical having from 4 to 12 carbon atoms, with the proviso that such alkyl radicals may contain one or two oxygen bridges, --O--, or a hydroxyl, amine, carboxylic acid, carboxylic acid ester, amide or imine group; a phenyl radical, a cyclohexyl radical, a cycloheptyl radical, a cyclopentyl radical, or a phenylalkyl, cyclohexylalkyl, cycloheptylalkyl or cyclopentylalkyl radical, the alkyl part of which comprises 1 to 4 carbon atoms; and with the further provisos that one or two of the substituents R6, R7 and R8 may be hydrogen atom; R6 may be an --NH2 group; R7 and R8 may together form, with the nitrogen atom from which they depend, a heterocycle which is saturated or contains one or several double bonds, or substituted such heterocycle bearing one or more alkyl substituents having from 1 to 4 carbon atoms; R6, R7 and R8 may together form with the nitrogen atom from which they depend, an unsaturated heterocycle, or a substituted such heterocycle bearing one or two methyl or ethyl substituents; R7 and R8 or R6, R7 and R8 may together form, with the nitrogen atom from which they depend, and with one or several additional nitrogen atoms and/or oxygen atoms, a saturated or unsaturated heterocycle, optionally substituted by one or several alkyl groups having from 1 to 4 carbon atoms; and R7 and R8 or R6, R7 and R8 may together form, with the nitrogen atom from which they depend, and optionally with one or several nitrogen atoms and/or oxygen atoms, a saturated or unsaturated polycyclic compound, optionally substituted by one or several alkyl groups having 1 to 4 carbon atoms.
Exemplary of such catalytically effective amines of formula (II), the following are representative:
(a) primary amines, such as n-propylamine, isopropylamine, isobutylamine, n-butylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methylbutylamine, n-hexylamine, 2-ethylhexylamine, aniline, laurylamine, cyclohexylamine, cyclopentylamine, benzylamine, guanidine, acetamidine, glycine ethyl ester, ethanolamine, ethylenediamine, hexamethylenediamine, N-aminoethylpyrrolidine, pyrazoline, lysine, N-aminoethylpyrrolidine, lysine, N-aminomorpholine and N-aminopiperidine;
(b) secondary amines, such as dibutylamine, dipropylamine, methylpropylamine, methylbutylamine, methylisobutylamine, methyltert-butylamine, methylbenzylamine, piperidine, diisopropylamine, diisobutylamine, ditert-butylamine, 1-methylcyclopentylamine, 1-methylcyclohexylamine, dicyclohexylamine, morpholine, imidiazole, pyrrolidine, imidazolidine, piperazine, and indole;
(c) tertiary amines, such as triethylamine, tributylamine, pyridine, tris(3,6-dioxaheptyl)amine and 1,8-diaza-bicyclo[5,4,0]7-undecene;
(d) ammonia;
(e) amino compounds such as hydrazine or its derivatives, in particular derivatives obtained by the substitution of one or two hydrogen atoms by alkyl, aryl, cycloaliphatic or heterocyclic radicals.
The catalytically effective amount of the amine used in the process of the invention may vary over very wide limits.
Typically it constitutes, by weight relative to the weight of the reaction mixture, from 0.005% to 5% thereof. Preferably, from 0.01 to 2.0% by weight of the amine relative to the reaction mixture will be employed, in order to provide sufficient efficacy, without using an excessive amount of the amine which does not concurrently permit any additional benefit or advantage.
Among the amines having the general formula (II), it is preferred to use primary or secondary amines of the general formula (III): ##STR3## in which R7 and R8, which may be identical or different, are each a hydrogen atom, with the proviso that both R1 and R8 are not hydrogen; a straight-chain alkyl radical having from 1 to 10 carbon atoms; a secondary alkyl radical having from 3 to 10 carbon atoms; a tertiary alkyl radical having from 4 to 10 carbon atoms; a cyclohexyl or cyclopentyl radical; a phenyl radical; or a benzyl or phenethyl radical;
R7 and R8 may alternatively form, together with the nitrogen atom from which they depend, and with another nitrogen atom and/or oxygen atom, a heterocycle which is saturated or which has one or several double bonds. Either or both R7 and R8 may contain one or several amine, hydroxyl or carboxylic ester groups.
Exemplary of primary amines of the general formula (III), n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methylbutylamine, n-hexylamine, 2-methylpentylamine, 3-methylpentylamine, 2-ethylhexylamine, laurylamine, cyclohexylamine, cyclopentylamine, benzylamine, glycine ethyl ester and ethanolamine are representative.
More particularly with regard to the secondary amines of the general formula (III), those in which at least one of the substituents R7 and R8, and preferably both substituents R7 and R8 are as follows, are even more especially preferred:
a secondary alkyl radical having from 3 to 10 carbon atoms, such as isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-octyl, 3-octyl, 4-octyl, 2-nonyl, 3-nonyl, 4-nonyl, 5-nonyl, 2-decyl, 3-decyl, 4-decyl and 5-decyl; a cyclohexyl or cyclopentyl radical.
Also especially preferred are heterocycles where R7 and R8 form, together with the nitrogen atom from which they depend, a heterocycle optionally containing another nitrogen or oxygen atom.
Exemplary of such secondary amines, diisopropylamine, diisobutylamine, dicyclohexylamine, morpholine and imidazole are representative.
Also preferred are hexamethylenediamine, N-aminoethylpyrrolidine, pyrazoline, N-aminomorpholine and N-amino piperidine.
The phenolic compounds of the formula (I), for which the subject process is most valuable, are those in which R2 is a chlorine atom, a fluorine atom or a bromine atom; a methoxy or ethoxy group; an aldehyde group; an OH group; a CN group; an acetoxy group; an ester group --COOR5, wherein R5 is a methyl or ethyl group; or an acyl group having from 2 to 4 carbon atoms; R1 is a hydrogen atom, a methyl, ethyl, propyl, isopropyl or tert-butyl group, or one of the substituents R2 ; at least one of R3 and R4 is a hydrogen atom, and the other either a hydrogen atom or one of the substituents R2.
Exemplary of the phenolic compounds of the formula (I), representative are: 4-chlorophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2-chloro-4-fluorophenol, 4-chloro-2-fluorophenol, 2-bromo-4-chlorophenol, 4-bromo-2-chlorophenol, 2-chloro-4-methoxyphenol, 4-chloro-2-methoxyphenol, 4-chloro-2-methylphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-hydroxyacetophenone, 4-hydroxybenzonitrile, 3-chloro-4-hydroxybenzaldehyde, and 5-chloro-2-hydroxybenzaldehyde.
The process according to this invention has several advantages.
One of these advantages is its intramolecular selectivity; when it is applied to a phenolic compound of formula (I) in which at least one of the meta-positions of the hydroxyl group is unsubstituted, essentially only the ortho-positions of the OH are chlorinated, whereas in the absence of the amine, a not insignificant amount of 3-chlorophenol or of the corresponding 5-chlorophenol is always formed, which is then very difficult to separate. Additionally, these compounds may be disadvantageous for certain applications.
Another very valuable advantage relates to the intermolecular selectivity of the process: if the process is employed with a mixture of a phenolic compound of formula (I) and one or more other phenolic compounds (such as, for example, position isomers of said phenolic compound of formula (I)) which do not correspond to the formula (I), it is mostly the phenolic compound of formula (I) which is chlorinated, whereas the other phenolic compound(s) are but slightly modified.
Thus, for example, the process of the invention may advantageously be applied to a mixture of 2,4-dichlorophenol and 2,6-dichlorophenol; 2,4,6-trichlorophenol is obtained from 2,4-dichlorophenol, whereas the 2,6-dichlorophenol, which is only slightly modified, may be relatively easily separated from the final reaction mixture.
It is also possible to use an industrial crude mixture containing 2,4-dichlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol, and thereby obtain, as before, 2,4,6-trichlorophenol and 2,6-dichlorophenol, which may be separated by fractional distillation.
Finally, another advantage of the subject process is the fact that the reaction of the gaseous chlorine and of the phenolic compound of the formula (I) is substantially complete, whereas, in the absence of the amine, a significant amount of the chlorine does not react. The problems of recycling of the excess chlorine, or of treating the gaseous effluents become less difficult to solve.
As a result, the amount of chlorine used in the process of the invention principally depends upon the desired degree of conversion of the phenolic compound (I).
The chlorine may be used as such, or diluted with an inert gas, such as, for example, nitrogen. The presence of an inert gas makes it possible, if required, to increase the rate of gas flow without increasing the amount of chlorine introduced over a given period of time.
The temperature at which the process of the invention is carried out is generally less than or equal to 150° C. Moreover, the lower limit of the temperature zone depends on the melting point of the phenolic compound (I), or mixture of phenolic compounds.
This temperature typically ranges from the melting point of the reaction mixture to 120° C., these limits, however, not being critical.
In order to further illustrate the present invention and the advantages thereof, the following specific examples are given, it being understood that same are intended only as illustrative and in nowise limitative.
The following materials were introduced into a 100-cm3 glass reactor equipped with a stirrer, a tube for the supply of chlorine gas, a thermometer and fitted with a condenser:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) diisopropylamine: 0.042 g (0.42 millimole, which was 0.1% by weight of the reaction medium).
The temperature was raised to 70° C. under stirring, such that the mixture was liquid and the introduction of gaseous chlorine was then initiated at a flow rate of 5 liters/hour.
The period for which the chlorination was carried out at 70° C. was 38 minutes, which corresponded to 3.15 liters of chlorine introduced (140.6 millimoles). The experiment was therefore carried out with an 8% excess of chlorine relative to 2,4-dichlorophenol.
Upon completion of the reaction, the entire equipment was purged with a stream of nitrogen. A reaction mass of 47.21 g was obtained, which was analyzed by gas chromatography in the presence of an internal standard.
The following results were obtained:
Degree of conversion (DC) of 2,4-dichlorophenol: 99.6%
Degree of conversion (DC) of 2,6-dichlorophenol: 6.6%
Yield (Y) of 2,4,6-trichlorophenol relative to the dichlorophenols converted: 100% ##EQU1##
The following materials were introduced into a 200-cm3 glass reactor equipped as indicated in Example 1:
(i) 2,4-dichlorophenol: 109.15 g (669.6 millimoles);
(ii) 2,6-dichlorophenol: 24.78 g (152 millimoles);
(iii) diisopropylamine: 0.13 g (1.29 millimole, which was 0.1% by weight of the reaction medium).
15 liters of chlorine (669.6 millimoles), which corresponded to the stoichiometric amount relative to the 2,4-dichlorophenol were introduced at 70° C., under stirring, at a flow rate of 5 l/h.
By chromatographic analysis upon completion of the chlorination, the following results were obtained:
DC of the 2,4-dichlorophenol: 99.95%
DC of the 2,6-dichlorophenol: 8.1%
Y of 2,4,6-trichlorophenol relative to the dichlorophenols converted: 99.1% ##EQU2##
The reaction was carried out as in Example 1 at 70° C., with a 50/50 mixture of 2,4-dichlorophenol and 2,6-dichlorophenol. The gaseous chlorine was introduced at a flow rate of 5 l/h and the amount introduced was such that the molar ratio of chlorine: 2,4-dichlorophenol was 0.95.
The following materials were introduced:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) diisopropylamine: variable amount (see Table 1);
(iv) chlorine: 2.765 liters (123 millimoles).
The characteristics of the different examples and the results obtained are reported in Table I:
TABLE I
__________________________________________________________________________
Diisopropyl-
DC of
DC of
amine the the DC of the
weight in g
2,4-
2,6-
Y of 2,4-DCP/DC
% by weight/
DCP DCP 2,4,6-TCP
of the
EXAMPLES
DCP (*) (**)
(***) 2,6-DCP
__________________________________________________________________________
Control
0 47.1%
38.6%
97.2% 1.2
experi-
ment A
Example 3
0.01 g 73.8%
10.0%
100% 7.4
0.0235%
Example 4
0.042 g
87.0%
4.7%
100% 18.5
0.10%
Example 5
0.094 g
82.2%
3.8%
100% 21.6
0.225%
Example 6
0.84 g 83.5%
7.2%
100% 11.6
2.0%
__________________________________________________________________________
(*) = DC of the 2,4dichlorophenol
(**) = DC of the 2,6dichlorophenol
(***) = Y of 2,4,6trichlorophenol
These experiments demonstrate the favorable effect of the amine used at very different amine/reaction mixture gravimetric ratios:
These experiments were carried out with different amines used at the same gravimetric concentration (0.02% relative to the dichlorophenols).
The reaction was carried out as in the series of Examples 3 to 6, using the following charges:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) amine: 0.02% by weight relative to the dichlorophenols;
(iv) chlorine: 2.766 liters (123 millimoles).
The characteristics of the different examples and the results obtained (Example 3 is repeated for comparison) are reported in Table II:
TABLE II
__________________________________________________________________________
DC of the
DC of
DC of 2,4-DCP/
the the Y of DC of the
EXAMPLES
Amine used
2,4-DCP
2,6-DCP
2,4,6-TCP
2,6-DCP
__________________________________________________________________________
Example 3
diisopropyl-
73.8%
10.0%
100% 7.4
amine
Example 7
methyl-n-
69.9%
15.8%
100% 4.4
butylamine
Example 8
dicyclohexyl-
76.9%
14.2%
99.0% 5.4
amine
Example 9
tributyl-
53.0%
33.1%
98.6% 1.6
amine
Example 10
tris(3,6-dioxa-
60.45%
25.1%
100% 2.4
heptyl)amine
Example 11
pyridine
60.4%
29.2%
97.6% 2.1
__________________________________________________________________________
At equal gravimetric concentration, a larger effect of the secondary amines relative to the tertiary amines was evidenced.
These experiments were carried out with three different amines, used at the same molar concentration (0.15% to 0.18% in moles relative to the dichlorophenols).
The reaction was carried out as in the series of Examples 3 to 6, using the following charges:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) amine: 2.766 liters (123 millimoles).
The characteristics of the different examples and the results obtained (Example 4 is repeated for comparison) are reported in Table III:
TABLE III
__________________________________________________________________________
Amine DC of the
% in moles/DCP DC of
Y of
2,4-DCP/
(% by weight/
DC of the 2,4,6-
DC of the
EXAMPLES
DCP) the 2,4-DCP
2,6-DCP
TCP 2,6-DCP
__________________________________________________________________________
Example 4
diisopropyl-
87.0% 4.7% 100%
18.5
amine
0.18% in moles
(0.1% by weight)
Example 12
dicyclohexyl-
89.0% 5.15%
99.4%
17.3
amine
0.18% in moles
(0.2% by weight
Example 13
tris(3,6-dioxa-
75.8% 17.25%
99.3%
4.4
heptyl)amine
0.155% in moles
(0.3% by weight)
__________________________________________________________________________
The reaction was carried out as in the series of Examples 3 to 6, using the following charges:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) diisopropylamine: 0.042 g (0.42 millimole, which is, 0.1% by weight relative to the dichlorophenols);
(iv) chlorine: 2.766 liters (123 millimoles).
The characteristics of the example and the results obtained (Example 4 is repeated for comparison) are reported in Table IV:
TABLE IV
__________________________________________________________________________
DC of the
Y of
2,4-DCP/
DC of the
DC of the
2,4,6-
DC of the
EXAMPLES
Temperature
2,4-DCP
2,6-DCP
TCP 2,6-DCP
__________________________________________________________________________
Example 4
70° C.
87.0% 4.7% 100%
18.5
Example 14
100° C.
88.3% 4.55% 99.9%
19.4
__________________________________________________________________________
The following materials were introduced into a 200-cm3 glass reactor equipped with a stirrer, a tube for the supply of gaseous chlorine, a thermometer and fitted with a condenser:
(i) 2,4-dichlorophenol: 100 g (613.5 millimoles);
(ii) diisopropylamine: 0.10 g (1 millimole, which was 0.1% by weight of the reaction medium).
The temperature was raised to 70° C., under stirring, such that the mixture was liquid and the introduction of gaseous chlorine was initiated at a flow rate of 5 liters/hour.
The period of chlorination carried out at 70° C. was 3 hours, which corresponded to 670 millimoles of chlorine introduced. The reaction was therefore carried out with a 10% excess of chlorine relative to the 2,4-dichlorophenol.
Upon completion of the reaction, the entire equipment was purged with a stream of nitrogen. A reaction mass was obtained, which was analyzed by gas chromatography in the presence of an internal standard.
The following results were obtained:
2,4-Dichlorophenol remaining: 0.09 g, which amounted to a DC of 99.9%
2,4,6-Trichlorophenol obtained: 119.69 g, which amounted to a Y relative to the 2,4-chlorophenol converted of 98.9%
2,4,5-Trichlorophenol concentration: less than 0.001% by weight in the reaction mass (estimated at 0.0007%).
Example 15 was repeated, with a twenty times higher concentration of diisopropylamine.
Thus, the following charges were used:
(i) 2,4-dichlorophenol: 100 g (613.5 millimoles);
(ii) diisopropylamine: 2.0 g (20 millimoles, which was 2% by weight of the reaction medium).
The following results were obtained:
2,4-Dichlorophenol remaining: 0.08 g, which amounted to a DC of 99.9%
2,4,6-Trichlorophenol obtained: 121.05 g, which amounted to a Y relative to the 2,4-dichlorophenol converted of 100%
2,4,5-Trichlorophenol concentration: less than 0.001% by weight in the reaction mass (estimated at 0.0004%).
The reaction was carried out as in the series of Examples 3 to 6, using the following materials:
(i) 2,4-dichlorophenol: 21.19 g (130 millimoles);
(ii) 2,6-dichlorophenol: 21.19 g (130 millimoles);
(iii) amine (see table): 0.042 g (0.1 by weight relative to the dichlorophenols);
(iv) chlorine (flow rate 5 l/h): Example 17=2.750 liters (123 millimoles)
(v) Example 18=2.910 liters (130 millimoles).
The characteristics of the two examples and the results obtained are reported in Table V.
TABLE V
__________________________________________________________________________
DC of the
Amine used Y of
2,4-DCP/
% by weight/
DC of the
DC of the
2,4,6-
DC of the
EXAMPLES
DCP 2,4-DCP
2,6-DCP
TCP 2,6-DCP
__________________________________________________________________________
Example 17
isopropyl-
87.45%
6.55% 98.7%
13.3
amine
0.1% by
weight
Example 18
n-propyl-
94.9% 6.8% 98.5%
13.9
amine
0.1% by
weight
__________________________________________________________________________
Example 15 was repeated without diisopropylamine.
In order to obtain a sufficient degree of conversion of the 2,4-dichlorophenol, a 60% excess of chlorine relative to the stiochiometric quantity should be introduced.
The following results were obtained:
2,4-Dichlorophenol remaining: 0.94 g, which amounted to a DC of 99.05%
2,4,6-Trichlorophenol obtained: 120.89 g, which amounted to a Y relative to the 2,4-dichlorophenol converted of 100%
2,4,5-Trichlorophenol concentration: 0.003% by weight in the reaction mass.
Control experiment B was repeated, but the supply of chlorine was terminated when the molar ratio of chlorine introduced/2,4-dichlorophenol added was equal to 1.1 (which represented a 10% excess of chlorine relative to the stoichiometric quantity).
The following results were obtained:
DC of 2,4-Dichlorophenol: 91.0%
Y of 2,4,6-Trichlorophenol: 100%
2,4,5-Trichlorophenol concentration: 0.0087% by weight in the reaction mass.
These experiments were carried out with different amines used with the same content by weight (0.1% relative to dichlorophenols).
The operation was performed as in Examples 3 to 6 with the following charges:
2,4-dichlorophenol: 21.19 g (130 millimoles)
2,6-dichlorophenol: 21.19 g (130 millimoles)
amine: 0.1% by weight relative to the dichlorophenols
chlorine: 2.766 liters (123 millimoles).
Table (VI) compiles the characteristics of the different examples, together with the results obtained.
TABLE (VI)
__________________________________________________________________________
DC of the
2,4-DCP/
Amine DC of the
DC of the
Y of DC of the
Examples
Used 2,4-DCP
2,6-DCP
2,4,6-TCP
2,6-DCP
__________________________________________________________________________
Example 19
morpholine
83.8% 7.4% 98% 11.3
Example 20
guanidine
77.3% 15.7% 98.5% 4.9
chlorhydrate
Example 21
acetamidine
81.0% 10.2% 100% 7.9
chlorhydrate
Example 22
imidazole
78.2% 13.4% 99% 5.8
Example 23
DBU.sup.(*)
71.9% 18.9% 98% 3.8
Example 24
glycine ethyl
79.2% 12.1% 99% 6.5
ester
Example 25
N--amino-
74.3% 12.7% 97.2% 5.8
morpholine
Example 26
N--amino-
68.8% 19.4% 98% 3.5
piperidine
Example 27
N--aminoethyl-
81.1% 10.3% 97.8% 7.9
pyrrolidine
Example 28
ethanolamine
84.6% 8.6% 98% 9.8
Example 29
benzylamine
82.1% 8.3% 98% 9.9
Example 30
ethylene-
61.3% 27.8% 98% 2.3
diamine
Example 31
L-lysine
63.7% 25.8% 96% 2.5
__________________________________________________________________________
.sup.(*) DBU = 1,8diazabicyclo[5,4,0]7undecene
While the invention has been described in terms of various preferred embodiments, the skilled artisan will appreciate that various modifications, substitutions, omissions, and changes may be made without departing from the spirit thereof. Accordingly, it is intended that the scope of the present invention be limited solely by the scope of the following claims, including equivalents thereof.
Claims (13)
1. A process for the selective chlorination, at a position ortho to a hydroxyl group thereof, of a phenolic compound having the general formula (I): ##STR4## in which R2 is hydrogen, an alkyl radical having from 1 to 4 carbon atoms, an alkoxy radical having from 1 to 4 carbon atoms, an acyloxy radical having from 2 to 4 carbon atoms, an acyl radical having from 2 to 4 carbon atoms, a carboxyl radical, an ester radical --COOR5, wherein R5 is a straight or branched chain alkyl radical having from 1 to 4 carbon atoms, a nitrile radical, an --OH radical, or a --CHO radical; R1 is hydrogen or one of the substituents R2 ; and R3 and R4, which may be identical or different, are each hydrogen or one of the substituents R2 ; comprising reacting said compound (I) with gaseous chlorine, in a solvent free, molten reaction medium and at a temperature no greater than about 150° C., in the presence of a catalytically effective amount of a primary, secondary or tertiary amine.
2. The process as defined by claim 1, said amine having the general formula (II): ##STR5## in which R6, R7 and R8, which may be identical or different, are each a straight chain alkyl radical having from 1 to 12 carbon atoms, a secondary alkyl radical having from 3 to 12 carbon atoms, or a tertiary alkyl radical having from 4 to 12 carbon atoms, with the proviso that such alkyl radicals may contain one or two oxygen bridges, --O--, or a hydroxyl, amine, carboxylic acid, carboxylic acid ester, amide or imine group, a phenyl radical, a cyclohexyl radical, a cycloheptyl radical, a cyclopentyl radical, or a phenylalkyl, cyclohexylalkyl, cycloheptylalkyl or cyclopentylalkyl radical, the alkyl part of which comprises 1 to 4 carbon atoms; with the further proviso that one or two of the substituents R6, R7 and R8 may be hydrogen; R6 may be an NH2 group; R7 and R8 may together form, with the nitrogen atom from which they depend, a heterocycle which is saturated or contains one or several double bonds, or a substituted such heterocycle bearing one or more alkyl substituents having from 1 to 4 carbon atoms; R6, R7 and R8 may together form, with the nitrogen atom from which they depend, an unsaturated heterocycle, or a substituted such heterocycle bearing one or two methyl or ethyl substituents; R7 and R8 or R6, R7 and R8 may together form, with the nitrogen atom from which they depend, and with one or several additional nitrogen and/or oxygen atoms, a saturated or unsaturated heterocycle, optionally substituted by one or several alkyl groups having from 1 to 4 carbon atoms; and R7 and R8 or R6, R7 and R8 may together form with the nitrogen atom from which they depend, and optionally with one or several nitrogen atoms and/or oxygen atoms, a saturated or unsaturated polycyclic compound, optionally substituted by one or several alkyl groups having 1 to 4 carbon atoms.
3. The process as defined by claim 2, the catalytically effective amount of said amine ranging from 0.005% to 5% by weight of the mixture of reaction.
4. The process as defined by claim 2, said amine having the general formula (III): ##STR6## in which R7 and R8, which may be identical or different, are each hydrogen, with the proviso that both R7 and R8 are not hydrogen, a straight chain alkyl radical having from 1 to 10 carbon atoms, a secondary alkyl radical having from 3 to 10 carbon atoms, a tertiary alkyl radical having from 4 to 10 carbon atoms, a cyclohexyl or cyclopentyl radical, a phenyl radical or a benzyl or phenethyl radical, R7 and R8 may together form, with the nitrogen atom from which they depend, and with another nitrogen atom and/or oxygen atom, a heterocycle which is saturated or which has one or several double bonds, either or both R7 and R8 may contain one or several amine, hydroxyl or carboxylic ester groups.
5. The process as defined by claim 4, said amine (III) being a secondary amine, in which at least one of the substituents R7 and R8 is a secondary alkyl radical having from 3 to 10 carbon atoms, or a secondary amine (III) wherein R7 and R8 form, together with the nitrogen atom from which they depend, a heterocycle optionally containing another nitrogen atom or an oxygen atom.
6. The process as defined by claim 5, in which at least one of the substituents R7 and R8 is isopropyl, 2-butyl, 2-pentyl, 3-pentyl, 2-hexyl, 3-hexyl, 2-heptyl, 3-heptyl, 4-heptyl, 2-octyl, 3-octyl, 4-octyl, 2-nonyl, 3-nonyl, 4-nonyl, 5-nonyl, 2-decyl, 3-decyl, 4-decyl, 5-decyl, cyclohexyl, cyclopentyl, morpholine, or imidiazole.
7. The process as defined by claim 2, said amine (II) being diisopropylamine, diisobutylamine or dicyclohexylamine.
8. The process as defined by claim 2, said amine (II) being n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, n-pentylamine, 2-methylbutylamine, 3-methylbutylamine, n-hexylamine, 2-methylpentylamine, 3-methylpentylamine, 2-ethylhexylamine, laurylamine, cyclohexylamine, cyclopentylamine, benzylamine, glycine ethyl ester, hexamethylenediamine, N-aminoethylpyrrolidine, pyrazoline, N-aminomorpholine N-aminopiperidine or ethanolamine.
9. The process as defined by claim 1, wherein said phenolic compound having the general formula (I), R2 is a chlorine, fluorine or bromine atom, a methoxy or ethoxy radical, an aldehyde radical, an OH radical, a CN radical, an acetoxy radical, an ester radical --COOR5, wherein R5 is a methyl or ethyl radical, or an acyl radical having from 2 to 4 carbon atoms;
R1 is a hydrogen atom, a methyl, ethyl, propyl, isopropyl, or tert-butyl radical, or is one of the substituents R2 ; and one of R3 and R4 is a hydrogen atom and the other either a hydrogen atom or one of the substituents R2.
10. The process as defined by claim 1, wherein said phenolic compound having the general formula (I) comprises 4-chlorophenol, 2,4-dichlorophenol, 3,4-dichlorophenol, 2-chloro-4-fluorophenol, 4-chloro-2-fluorophenol, 2-bromo-4-chlorophenol, 4-bromo-2-chlorophenol, 2-chloro-4-methoxyphenol, 4-chloro-2-methoxyphenol, 4-chloro-2-methylphenol, 4-methoxyphenol, 4-ethoxyphenol, 4-hydroxyacetophenone, 4-hydroxybenzonitrile, 3-chloro-4-hydroxybenzaldehyde, or 5-chloro-2-hydroxybenzaldehyde.
11. The process as defined by claim 1, wherein said phenolic compound having the general formula (I) comprises mixture of 2,4-dichlorophenol and 2,6-dichlorophenol.
12. The process as defined by claim 1, wherein said phenolic compound having the general formula (I) comprises mixture of 2,4-dichlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol.
13. The process as defined by claim 1, carried out at a temperature from the melting point of the reaction mixture to 120° C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8514093A FR2587332B1 (en) | 1985-09-19 | 1985-09-19 | PROCESS FOR THE SELECTIVE CHLORINATION OF PHENOLIC COMPOUNDS |
| FR8514093 | 1985-09-19 | ||
| EP86.420221.3 | 1986-09-03 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06909177 Continuation-In-Part | 1986-09-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4876396A true US4876396A (en) | 1989-10-24 |
Family
ID=9323165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US07/078,771 Expired - Lifetime US4876396A (en) | 1985-09-19 | 1987-07-28 | Selective chlorination of phenols |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4876396A (en) |
| EP (1) | EP0216714B1 (en) |
| AT (1) | ATE76053T1 (en) |
| DE (1) | DE3685281D1 (en) |
| FR (1) | FR2587332B1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026926A (en) * | 1987-03-05 | 1991-06-25 | Rhone-Poulenc Chimie | Chlorination of ortho-chlorophenol |
| US5045547A (en) * | 1989-03-14 | 1991-09-03 | Bayer Aktiengesellschaft | Leukotriene-inhibiting substituted (quinolin-2-yl-methoxy)phenyl-N,N'-sulphonylureas and use thereas |
| US5426243A (en) * | 1994-08-17 | 1995-06-20 | Albemarle Corporation | Process for preparing 1,6-dibromo-2-naphthylene compounds |
| US5847236A (en) * | 1995-10-02 | 1998-12-08 | Bayer Aktiengesellschaft | Process for the preparation of 2-chloro-4-methylphenol |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2601001B1 (en) * | 1986-07-02 | 1988-11-10 | Rhone Poulenc Chim Base | PROCESS FOR THE CHLORINATION OF PHENOLIC COMPOUNDS |
| FR2611706B1 (en) * | 1987-03-05 | 1989-06-16 | Rhone Poulenc Chimie | PROCESS FOR THE CHLORINATION OF NITROPHENOLS |
| FR2611701B1 (en) * | 1987-03-05 | 1989-06-16 | Rhone Poulenc Chimie | PROCESS FOR THE CHLORINATION OF PHENOLIC COMPOUNDS |
| IE62463B1 (en) | 1988-07-07 | 1995-02-08 | Res Dev Foundation | Immunoconjugates for cancer diagnosis and therapy |
| FR2764884B1 (en) * | 1997-06-24 | 1999-09-10 | Rhodia Chimie Sa | PROCESS FOR THE CHLORINATION OF HALOGENATED PHENOLS |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237321A (en) * | 1977-12-06 | 1980-12-02 | Sterling Drug Inc. | 2,4,5-Trichlorophenol process |
| DE3318791A1 (en) * | 1982-05-26 | 1983-12-01 | CIBA-GEIGY AG, 4002 Basel | Process for the preparation of 2-chlorophenol |
| GB2135310A (en) * | 1983-02-23 | 1984-08-30 | Coalite Group Plc | Preparation of halogenated phenols and salts thereof |
| EP0196260A1 (en) * | 1985-03-12 | 1986-10-01 | Rhone-Poulenc Chimie | Process for the selective chlorination of phenolic compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR920514A (en) * | 1943-04-21 | 1947-04-10 | Ici Ltd | Manufacture of chlorinated organic compounds |
| CH630593A5 (en) * | 1977-08-26 | 1982-06-30 | Ciba Geigy Ag | METHOD FOR PRODUCING 4-BROM-2-CHLORPHENOL. |
| JPS5540613A (en) * | 1978-09-14 | 1980-03-22 | Sumitomo Chem Co Ltd | Preparation of 2, 6-dichloro-4-alkylphenol |
-
1985
- 1985-09-19 FR FR8514093A patent/FR2587332B1/en not_active Expired
-
1986
- 1986-09-03 EP EP86420221A patent/EP0216714B1/en not_active Expired - Lifetime
- 1986-09-03 AT AT86420221T patent/ATE76053T1/en not_active IP Right Cessation
- 1986-09-03 DE DE8686420221T patent/DE3685281D1/en not_active Expired - Fee Related
-
1987
- 1987-07-28 US US07/078,771 patent/US4876396A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4237321A (en) * | 1977-12-06 | 1980-12-02 | Sterling Drug Inc. | 2,4,5-Trichlorophenol process |
| DE3318791A1 (en) * | 1982-05-26 | 1983-12-01 | CIBA-GEIGY AG, 4002 Basel | Process for the preparation of 2-chlorophenol |
| GB2135310A (en) * | 1983-02-23 | 1984-08-30 | Coalite Group Plc | Preparation of halogenated phenols and salts thereof |
| EP0196260A1 (en) * | 1985-03-12 | 1986-10-01 | Rhone-Poulenc Chimie | Process for the selective chlorination of phenolic compounds |
Non-Patent Citations (2)
| Title |
|---|
| Nodera et al., "Chemical Abstracts", vol. 93 (1980), p. 93:239023s. |
| Nodera et al., Chemical Abstracts , vol. 93 (1980), p. 93:239023s. * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026926A (en) * | 1987-03-05 | 1991-06-25 | Rhone-Poulenc Chimie | Chlorination of ortho-chlorophenol |
| US5045547A (en) * | 1989-03-14 | 1991-09-03 | Bayer Aktiengesellschaft | Leukotriene-inhibiting substituted (quinolin-2-yl-methoxy)phenyl-N,N'-sulphonylureas and use thereas |
| US5426243A (en) * | 1994-08-17 | 1995-06-20 | Albemarle Corporation | Process for preparing 1,6-dibromo-2-naphthylene compounds |
| US5847236A (en) * | 1995-10-02 | 1998-12-08 | Bayer Aktiengesellschaft | Process for the preparation of 2-chloro-4-methylphenol |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0216714B1 (en) | 1992-05-13 |
| DE3685281D1 (en) | 1992-06-17 |
| FR2587332A1 (en) | 1987-03-20 |
| EP0216714A3 (en) | 1988-11-17 |
| FR2587332B1 (en) | 1989-02-17 |
| ATE76053T1 (en) | 1992-05-15 |
| EP0216714A2 (en) | 1987-04-01 |
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